Dye transfer acceleration with polyamine compounds

ABSTRACT

Monochromatic or polychromatic color photographs can be quickly and simply obtained by a color development dye transfer method in which color photographic material is subjected to development dye transfer in the presence of at least one of polymethylenepolyamine derivatives having the general formula,   WHEREIN R is a hydrogen or a lower alkyl group and n, p and q are individually a positive integer of from 1 to 9, 2 to 4 and 1 to 4, respectively.

United States Patent Ohyama et al. June 3, 1975 [54] DYE TRANSFER ACCELERATION WITH 3,173,786 3/1965 Green et al. 96/29 D POLYAMINE COMPOUNDS 3,698,896 l0/1972 Abbott 96/3 3,718,464 2/1973 .lanssen et al 96/29 D [75] Inventors: Yasushi Ohyama; l-lideo Sumitani,

both 0f Nagaokakyo Japan Primary ExaminerNorman G. Torchin [73] Assignee: Mitsubishi Paper Mills, Ltd., Tokyo, Ass s ant ExaminrRiChard L. Schilling Japan Attorney, Agent, or FirmCushman, Darby &

h 221 Filed: Jan. 3, 1973 I Monochromatic or polychromatic color photographs [30] Foreign Application Priority Data can be quickly and simply obtained by a color devel- Jan. 7, I972 Japan 47-4528 opment dye transfer method in which color photo graphic material is subjected to development dye Cl 96/29 /55; transfer in the presence of at least one of polyme- 96/66 63; 7 thylenepolyamine derivatives having the general for- [51] Int. Cl. G03c 5/54; G03c 7/00; G03c 5/30; mula,

G030 H40 [58] Field of Search 96/77, 3, 29 D, 107, 66 R, H CH CH NH 96/66.3,55R 2 i 2)P](q 17 2 R [56] References Cited UNITED STATES PATENTS wherein R is a hydrogen or a lower alkyl group and n, 2 91 037 2 1940 Mamas et 1 I I I M 9 55 p and q are individually a positive integer of from 1 to 2,515,147 7/1950 Wasley 96/55 9, 2 to 4 and l to 4, respectively. 2,518,698 8/1950 Lowe et a1... 96/l07 I 2,857,275 lO/1958 Land et a1 96/66 R 7 Clalms, 3 Drawing Figures PATENTEDJUH 3 1915 35397. :37

SHEET 2 FIG. 2

E 0.4 (IO%EtOH) 2 II E iq v 2 n 2 0 Z N 0.5 p O 20 E O P g 0.6 E '6 1 g 3 E O.8 g 2 r0 0/ O9 6 E l0 E IQ LL H r w (H20) O 3 B -|.5 g N D? O Q 0 2 2 2 05 j m "5 m 1 fi 4 5e%89|ou|2 NUMBER OF CARBON CHAIN OR CORRESPONDING CARBON CHA'N (l.l2diomino)-dodecane(Cm) 9 IS DESENSITIZED EVEN WITH IOAEtOH DYE TRANSFER ACCELERATION WITH POLYAMINE COMPGUNDS' This invention relates to an improvement in a known photographic process to which a color development dye transfer method has been applied for obtaining a monochromatic or polychromatic color photograph quickly and simply, and the invention aims to accelerate the development dye transfer rate of the process, to complete the color development dye transfer treatment in a short period of time, and to obtain a beautiful color photographic image excellent in gradation.

The color development dye transfer method according to the present invention differs from the conventional color development in the specificity of the color couplers used and in the utilization of a dye transfer layer containing a mordant for an anionic dye. Two types of non-diffusible color couplers exist as mentioned below, both of which utilize a so-called elimination coupling reaction and split off diffusible anionic dyes by color development.

Non-diffusible color couplers of one type are such that a so-called ballast group containing a long chain group has been introduced into the coupling position of a molecule of a known color coupler through a diazo, sulfo, methine or the like group which may be cut by coupling, and sulfone or carboxyl group have been introduced into other position. These couplers individu ally forrn cyan and magenta diffusible dyes as shown below.

(Silver halide) (Cyan-colored diffusible dyel Choc n 2A3; t

(Ballast fast to d1. l sion) 11 Yellovwcolcrei non-diffusible coupler developing ragenta color) The couplers themselves have yellow to yellowish orange colors. However, as a yellow color-developing coupler, a colorless coupler is preferable because yellow color may disturb the sensitivity and the gradation of a blue-sensitive emulsion used. An example of such colorless coupler is as shown below.

Q-co-ca-cn-tta 501.118

(Colorless n n-diffusible coupler" developing yellow color Like in the above lYellow-cclcred ilffusic in; nondlffusl'cle (Yellow coloroff ellcw aye (Yellow colored non-ilfius ible dye l C HE (Yellow-colored diffusible dye] Alternatively, there is such an example as shown below.

(Non-diffwi'cle coupler splitting (Developing agent I (Non-diffusib la phenazine "lye I ZAg ZHX \Dlffusible crap '5 colored aye) This example is specific in that it forms a phenazine dye, but is identical with the aforesaid example in that the portion separated by coupling becomes an anionic diffusible dye, and hence utilized in the present invention.

In any way, the anionic dye thus formed is a kind of acid dye, and hence diffuses in an aqueous medium. Accordingly, in case a suitable mordanting agent has been incorporated into a transfer layer which may be situated adjacent to the photosensitive emulsion layer, the said dye difiuses into the dye transfer layer and is firmly fixed there. This process is identical with the color photographic process according to dye transfer which is called an imbibition or dye transfer process. As the mordanting agent, an inorganic colloidal precipitate such as aluminum hydroxide or magnesium hydroxide was used before. Recently, however, such an organic nitrogen-containing compound as quaternary ammonium salt, pyridinium salt or picolinium salt, or a guanidine derivative has come to be used as well. Among these, predominantly excellent mordanting agents are cationic polymers comprising the abovementioned nitrogen-containing organic compounds. Examples of such mordanting agents are poly-2- vinylpyridine (I), poly-4-vinylpyridine or a quaternary salt thereof (ll), many polymers of chain or cyclic ammonium salts (III to X), and aminoguanides of vinyl polymers or starch oxides (XI to Xlll). Structural formulas of typical mordanting agents are as shown below.

2 CHg CHCH2 ca 1 l l l cs ca i O c N c 01-2 1 i l 1 CH2 CH2 i NH 2* l 01 NH i (X) (XI) E CH3 coon CH CH CH2 CH-CHQ-CH CH2 CH CH2 ca (XIII) The above-mentioned cationic polymer may be incorporated as it is into such a dye transfer layerforming hydrophilic colloidal binder as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, starch or a derivative thereof. Alternatively, the said polymer may be incorporated as a fine coaservate, which is formed by reacting the polymer in an aqueous medium with gelatin, polyvinyl alcohol or a phthalic derivative of starch. Ordinarily, the amount of the polymer is about 0.] to 1.0 g. per in of the finished dye transfer layer.

On the other hand, a photosensitive material is prepared by coating on a support one or more silver halide layers containing a coupler capable of splitting off the aforesaid anionic dye. After proper exposure, the thus prepared photosensitive material is superposed face to face on a dye transfer sheet having a dye transfer layer which has sufficiently been coated with a viscous developer. Alternatively, the two sheets are individually dipped in a developer for about seconds so as to sufficiently absorb the developer, and then the photosensitive material is superposed face to face on the dye transfer sheet. When the resulting photographic mate rial is allowed to stand after slight squeezing, exposed silver halide in the photosensitive material is developed and, at the same time, an anionic dye, which is formed by the aforesaid coupling reaction, diffuses from the photosensitive emulsion layer to the dye transfer layer. In this dye transfer layer, the anionic dye is captured by a cationic polymer, which is the mordanting agent, to form a complex, with the result that the anionic dye is deprived of its diffusibility and is fixed. Accordingly, when the photosensitive material is peeled off from the dye transfer sheet, a desired color photographic image is obtained in the dye transfer layer. However, in case a color developer for the development of ordinary color film or color print is used, the photographic material shows no sufficient density and gradation, unless it is allowed to stand at normal temperature (20 to 25C.) for 5 to 10 minutes. It is said that phenidone or Metol displays a high accelerating effect when used at a concentration of about 0.2 g/liter in an ordinary color developer [refer to L. F. A. Mason: Journal of Photographic Science, Vol. ll (l963), pages 136 139]. According to experiments conducted by the present inventors, however, both phenidone and Metol merely decreased the apparent sensitivity and did not show any effect of accelerating the development but rather inhibited the development. As one of the present inventors previously clarified in the development of a closed system, in which was used a combination of silver complex salt diffusion transfer method and color development [refer to Yasushi Ohyama and Sadayuki Miyazawa: Bulletin of Society of Scientific Photography of Japan, Vol. 19 (1969), pages 4 to 10], it is well known that in the case of a color developer containing a small amount of sodium thiosulfate (pentahydrate, 0.5 to 10 g/liter), the color density of a negative subjected to color development increases when phenidone or Metol is added in a larger amount (0.2 to 2.0 g/liter). In the color development according to the present invention, in which is splitted off such diffusible anionic dye as mentioned tetramine,

previously, it has been clarified that only in the case where sodium thiosulfate is added and any of phenidone. Metol and hydroquinone is added in an amount of 0.1 to 0.5 g/liter. the development dye transfer is accelerated and the density of transferred dye increases to increase the apparent sensitivity. This effect, however, cannot be said to be a practically important development accelerating effect, because the increase in apparent sensitivity is not more than about 0.3 to 0.4 in terms of a logarithmic value and fog is formed in large amount (refer to Example 4 set forth later).

In the ordinary black-white development using hydroquinone or like developing agent, which shows an anionic property at an alkaline pH and which is liable to undergo the influence of potential barrier due to adsorption of halogen ions on the surfaces of silver halide particles, there is used as a accelerator such a cationic onium salt as, for example, tetrabutylammonium bromide or N-(B-phenethyll-methylpyridinium p-toluenesulfonate. The above-mentioned accelerator appears to be effective (refer to, for example. U.S. Pat. No. 3,173,786) in the Polacolor" process (registered tradename of a l minute-color photographic process invented by Polaroid Co. USA.) in which is used the so-called dye-developer of such a type that hydroquinone molecules have been bonded to dye molecules by means of ethylene molecules). in the process of the present invention, the developing agent used is a paminoaniline derivative, which does not undergo the influence of potential barrier of silver halide particles. Accordingly. the accelerator is entirely ineffective, or rather inhibits the development. in some cases, though this is a matter of course.

On the other hand, B-phenylethylamine, which is well known as an accelerator for the ordinary color development. is also low in effectiveness in the color development dye transfer process according to the present invention in which a diffusing anionic dye is separated, and shows an apparent sensitivity increase of only 0.1 to 0.2 in terms ofa logarithmic value. Likewise, various alkyl-, arylor aralkyl-amines, which are said to be effective in the ordinary color development. are also ineffective or inhibitory. and no accelerator capable of ef fectively accelerating the development dye transfer has not been discovered yet. However, it has been found that diaminoethane, diaminopropane. diaminobutane, diaminohexane, diaminoheptane. diaminooctane, diaminononane, diaminodecane, diaminododecane and the like diaminoalkanes and polymethylenediamines can greatly accelerate the development dye transfer. in general, unlike the monoamines. It has also been found that diethylenetriamine. triethylene' tetraethylenepentamine. dipropylenetria mine. tripropylenetetramine. tetrapropylenepentamine and dipropylenebutylenetetramine (another name: spermine) formed by connecting the molecules of said ethylenediamine. propylenediamine, butylenediamine, etc. are also effective.

The former accelerators are mostly those which cor respond to the formula NH (CH ),,-NH However, there are also such diaminopropanes corresponding to the above-mentioned formula as, for example, 1,3 diaminopropane (NH -CH -CH -CH --NH and l,2diaminopropane (Nik -Eli sll lfi i l Generally, therefore, the former accelerators can be represented by the formula which may be abbreviated to On the other hand, the latter accelerators have such structural formulas as shown below which are arranged in the above-mentioned order.

NH (CH NH(CH NH(CH NH The accelerating effect does not increase even when the number of the chain NH(CH ),,NH is increased, as will be mentioned later, but has a definite limit. Further, other accelerators than those mentioned above are not only difficulty synthesizable but also scarcely occur in nature, and hence are expensive and cannot be used in practice. Summarizing the above, it has been found that substances having the structural a irca ,NH

Phi -1,

(which may be called polymethylenepolyamine derivatives) are effective as accelerators for the development dye transfer according to the present process. In the above formula, R is a hydrogen atom or a lower alkyl group, and n. p and q are positive integers, and it has also been found that the substances are practically effective when n is l to 9, p is 2 to 4 and q is l to 4. In the above. the effective substances have collectively been defined. The relation between the number of carbon chains and the effectiveness will be mentioned in detail later. Further, alcohols themselves have no accelerating effects at all and are rather inhibitory, but can greatly increase the effects when used in combination with the aforesaid substances and hence are extremely useful, as will be mentioned later. There might be some other substances which are similar in supplemental effects to those mentioned above. In the present invention, however, the accelerators have been limited to substances which are substantially effective.

The fact mentioned below is quite unexpected.

That is, it is well known that the aforesaid polymethylenepolyamine as a sensitizer for silver halide emulsion is added in such a slight amount as 5 to 50 mg. per mole of silver halide which is 170 g. in terms of AgNO (refer to US. Pat. Nos. 2,518,698 and 2,743,182). In the case of an ordinary photosensitive material, the amount of silver halide coated thereon is about 1 to 10 g/m in terms of AgNO Accordingly, the amount of the above-mentioned sensitizer is as minute as 0.03 to 0.3 mg/m 0.00003 to 0.0003 g/m). This amount is not comparable to the amount of sensitizer or accelerator required for the accelerator of development dye transfer according to the present invention which is 0.03 to 2 g/m as will be mentioned later. If such a large amount of sensitizer is added to the emulsion, fog is formed in a markedly large amount. It is therefore natural that the effect of the present invention has not been found hitherto. Further, US. Pat. No. 2,518,698 discloses in column 1, lines that triethylamine or triethanolamine is effective as a sensitizer. As mentioned previously, however, it has been found that in the present invention, the above-mentioned substances do not show any accelerating effect at ail, and ethylenediamine, which has been concluded to be ineffective as a sensitizer, is effective and has the same effect as that of dipropylenetriamine. The above fact cannot easily be thought out from the conventional knowledge.

The development dye transfer accelerating mechanism of the aforesaid substances has not been elucidated yet, but is not a mere phenomenon of accelerating the color development, as is clear from the abovementioned fact that substances, which have been effective hitherto, are ineffective or scarcely effective. The present inventors consider that the said substance complexes with an anionic dye (the amino group forms a salt together with the anion group) to take such a form as to be easily movable in gelatin or the like colloidal binder in an aqueous medium less in ionic property, and the substance acts as a carrier for the dye molecules to bring the dye quickly from the circumference of silver halide, in which the dye has been formed, to the dye transfer layer, with the result that the color development itself is accelerated. One of the reasons therefor is the elfect of addition of alcohol. That is, in case alcohol is added to the system, the development is rather inhibited if the accelerator polymethylenepolyamine issabsent but is accelerated to a great extent if the said accelerator is present. The substance, which is effective in the above case. includes not only l,8-diaminooctane and l,6-diaminohexane which are difficulty soluble in alcohol or water but also 1,2- diaminoethane and 1,3-diaminopropane which are more easily soluble in water rather than in alcohol. it may be said that the development dye transfer accelerator mechanism of such substances cannot be explained at present, unless the above-mentioned hypoth esis of carrier is adopted.

The present inventors investigated low molecular weight guanidines which have a property of forming complexes together with anionic dyes, like the polyamines. As the result, the inventors have found that the guanidines are markedly different from the polyamines, since they are ineffective or tend to inhibit the development, like the aforesaid cyclic monoamines, pyridine, cyclohexylamine and piperazine. Considering the fact that when used in dyeing, both the polyamines and the guanidines act as fixing agents for anionic dyes, it is understood that the development accelerating effects of said substances cannot be easily inferred and that the actions of the polymethylenepolyamines used in the present invention are quite unique.

The effects of development dye transfer will be examined in more detail below.

FIG. 1 is a graph showing the relation between concentrations and apparent sensitivity increase values (AS) of l,n-diaminoalkanes in processing solutions.

FIG. 2 is a graph showing the relation between carbon chain numbers (n) of l, n-diaminoalkanes [NH (CH ),,NH ]and limiting effective concentr tions thereof in the case where alcohol is not added to the developer (H O system) and in the case where alcohol is added to the developer (10 EtOH system) which are obtained from FIG. I, in addition to the relation between corresponding carbon chain numbers and limiting effective concentrations of other polymethylenepolyamines.

FIG. 3 is a graph showing the variation in characteris tic curves of magenta dye due to prolongation of the development dye transfer time in the case where the developer used has not been incorporated with acceler ator, in comparison with the variation in characteristic curves of magenta dye in the case where the development dye transfer is effected for 2 minutes in the presence of varying amounts of 1,6-diaminohexane as accelerator.

As shown in the drawing (FIG. 3) for illustration of Example I, the case where the development dye transfer time is prolonged and the case where the dye transfer treatment is effected for a definite short period of time naturally differ from each other with respect to the state of variation in characteristic curve of the ac celerator used. Both the case where the time is prolonged and the case where the amount of accelerator is increased are common to each other in that the characteristic curves of the accelerator used gradually move to the left side (in the direction less in amount of exposure) and in that the apparent sensitivity increases and the maximum density tends to increase. As to the apparent sensitivity increase, the effect of accelerator in the case where the amount of accelerator is increased in identical with or more than that in the case where the time is prolonged, whereas as to the maximum density, the former effect does not always compensate the latter effect. However, it may be said that the effect of accelerator in the above case is quite satisfactory because in the case of a color print having three color layers, it is sufficient that the maximum reflective density of one color is l.2 (the maximum reflective density of black color formed from the three colors becomes 2.5 or more).

The apparent sensitivity increase is not the actual sensitivity increase, because the accelertor is not present at or before the time of exposure but is added to the system at the stage of development dye transfer, and is used for the reason that the characteristic curve moves to the left like in the case where the development time is prolonged or the liquid temperature is increased. In case the amount of characteristic curve, which has moved to the left in parallel to the axis of log E (logarithm of exposure amount) of the characteristic curve at a definite density (e.g. a reflective density of 0.5 to 0.8), is deedmed as the apparent sensitivity increase (AS), the effect of the accelerator can be evaluated from the value of said (AS).

On the other hand, it is also important to contrast the amount of accelerator and the effect thereof. It is desirable to use a accelerator which is effective even when used in a small amount, but there is an accelerator which, despite of its being effective even when used in a small amount, is not increased in effect even if the amount thereof is increased. Further, when the amount of accelerator is increased, the amount of fog is also increased, in general. However, there is also an accelerator which makes the amount of fog greater before the effect thereof has not sufficiently been displayed, or an accelerator which is increased in effect but do not increase the amount of fog. Thus, the relation between the effect of accelerator and the amount of fog formed should also be taken into consideration. Furthermore, the effect of accelerator is greatly affected by the conditions adopted, i.e. the composition of developer used, the composition of photosensitive material, particularly the kind and amount of coupler, and the treatment temperature. Accordingly, it is impossible to conclude which compounds are excellent among those mentioned previously. However, there is an interesting relation between the minimum density, at which the accelerating effect is first displayed, and the chemical structure of accelerator, so that the scope of effective substances can be spontaneously limited by taking the abovementioned relation into consideration.

That is, compounds having the most simple formula NH -(CH ),,Nl-I are tested in development accelerating ability at several stages while varying the concentrations thereof like in Example 1 to measure the relation between the apparent sensitivity increase (AS) and the logarithm of molar concentration. As the result, all the compound show a linear relation within a definite range, as shown in FIG. 1. From the intersecting point of said linear line and the horizontal axis, there is calculated the minimum to the limiting concentration will be referred to as limiting effective concentration," hereinafter).

The five lines at the lower part of FIG. 1 show the cases where the substances of the above-mentioned formula. in which n is 2, 3, 4, 6 and 8, are individually added to a developer containing no alcohol. From the said lines, it is understood that the limiting effective concentration markedly decreases with increasing carbon chain. That is, the compound C is effective even when used in l/lO the amount of the compound C but tends to be rather lowered in AS value, which is the absolute value of effect. For example, when 1,3- diaminopropane (C n=3) and l,6-diaminohexane (C =6) are compared with each other, the latter is more excellent in case the concentration is 10 mM, whereas the former is higher in effect in case the concentration is 30 mM, and thus is more advantageous since it is easily soluble and inexpensive. When the said substance is used at a concentration of 50 mM or more, fog is undesirably formed in case the dye transfer treatment time is 2 minutes. However, when the treatment time is shortened to about 1 minute to l minute and 30 seconds, no fog is formed and a print sufficient in density and gradation can be obtained.

On the other hand, the five lines at the upper left portion of FIG. 1 show the cases where a part of the solvent of the development dye transfer processing solution has been substituted with an alcohol l ethanol solution). An accelerator having or more carbon chains is scarcely soluble in water, and therefore the alcohol should necessarily be added. The activity of l,lO-diaminodecane (n=l0) is not so great. When the alcohol is added, the said compound is markedly increases in accelerating ability, regardless of the number of carbon chains, with the result that not only the limiting effective concentration decreases from 1/5 to l/ but also the value of apparent sensitivity increase (AS) itself increases to a great extent.

When the relation between activity and number of carbon chains (n) of individual compounds is investi gated, using a reciprocal of the limiting effective concentration as a measure for measuring the activity, there are obtained such results as represented by the white and black circles shown in FIG. 2. That is, both in the case where the alcohol is added (black) and in the case where the alcohol is not added (white), the activity increases in proportion to n, reaches maximum when n is about 8, and thereafter quickly lowers with decreasing solubility and, in the case where n is 12, the development dye transfer is greatly inhibited even when the alcohol has been added.

When the relation between number of carbon chains and limiting effective concentration of individual compounds is measured from the relation between AS and concentration as shown in FIG. 1, counting the number of CH and NH groups present between the initial Nl-I group to an optional NH (or NH group (considering as if NH is also a carbon chain), assuming that the probabilities of appearance in every case would be identical with each other), and considering that the average value of effective carbon chain number is corresponding carbon chain, there are obtained such results that triamines show such relations as represented by the white and black triangles shown in FIG. 2 and tetramine shows such relation as represented by the square shown in FIG. 2. Thus, most of the compounds follow the above-mentioned tendency (it is considered that the existence, if any, of compounds which do not completely follow the said tendency might probably be ascribable to the unsuitableness of the said assumption that probabilities would be identical with each other). This is quite surprising. The fact that an accelerator is not increased in effect even when the number of NI-l- (CH ),,NH is increased is well connected to the fact that the corresponding carbon chain number of the accelerator becomes 8 or more. It is considered that even if an accelerator is actually increased in number of carbon chains and of Nl-I groups, the accelerator is increased in adsorptivity for silver halide and involves the silver halide to disturb the development with the result that the accelerator is decreased in activity or inhibits the development. It is therefore clear that accelerator within the scope of the aforesaid general formula are important, in practice.

In the above, the molecular structure of accelerators which are successfully usable in the present invention and the preferable amounts of said accelerators have substantially been explained. From FIG. 1, it is clear that the preferable amounts of simple diamines of the formula NH (CH ),,NH are within such a broad range as from about 1 mM to 50 mM. From FIGS. 2 and 3, it is understood that other polymethylenepolyamines may also be used in such amounts as above, since they are identical in limiting effective concentration with the said diamines. An accelerator high in limiting effective concentration has such a low molecular weight as 60 to 75, while an accelerator low in limiting effective concentration has such a considerably high molecular weight as to 150. It is therefore easily understood that at a practical concentration in a development dye transfer processing solution, the accelerator may be used, as being compensated with the molecular weight thereof, in such a proportion as 0.15 to 3.0 g/liter, Le. a molar concentration within the range of 1:20, which is somewhat narrower than the range of l:50.

As mentioned previously, most of the polyamines used in the present invention are strong sensitizers and,

when used in large amounts, tend to act as foggants for silver halide emulsions. Accordingly, it is impossible to introduce them directly into photosensitive emulsion layers, However, the accelerator can be freely incorporated into the mordanting agent-containing colloidal binder layer of a dye transfer material or into a layer adjacent thereto. When this procedure is adopted, there is brought about such advantage that a suitable amount of the accelerator can be accurately fed during the development dye transfer treatment without adding the accelerator to the development dye transfer processing solution. Further, there are such effects that not only can the processing solution be prepared easily and conveniently but also it can be stored for longer periods of time.

In this case, the processing solution is ordinarily disposed between the photosensitive material and the dye transfer material of a photographic material which have been individually coated on separate supports as set forth in Example 1 shown later and which have been contacted face to face with each other. The amount of the processing solution varies depending on the extent of squeezing of the photographic material and the liquid absorption properties of the photosensitive material and the dye transfer material, and hence is not definite. However, generally from 100 to 200 ml/m of the processing solution is present between the two during the treatment. In case the processing solution is desired to be spread to a definite thickness between the dried faces of the two by the aid of precise roller and frame and according to a process similar to the known one minute-photographic treatment of Polaroid, the said thickness is ordinarily brought to 0.05 to 0.10 mm.(= 0.0020 to 0.0036 inch). It is therefore understood that the amount of the processing solution becomes 50 to 70 ml/m and the concentration of the processing solution is required to be 2 to 3 times the concentration of the solution used in Example 1. However, the required amount of the accelerator per unit area may be deemed as being identical with that in Example 1. In any way, the accelerator in the above case requires a longer dissolving-out time than in the case where it is added to the developer, and does not reach an equilibrium concentration in a short period of time, so that the accelerator should have been added in excess as much. That is, the accelerator is required to be added in a considerably larger amount than 0.0l5 to 0.60 g/m which is a value obtained by simply calculating the amount of the accelerator in the above-mentioned processing solution into the amount thereof per unit area. The amount of each accelerator varies depending on the thicknesses of water absorption layers of photosensitive material and dye transfer material, the treatment procedure and the treatment time, but is required to be 2 to 3 times the above-mentioned value, and may collectively be 0.03 to 2.0 glm It is, of course, possible to transfer not only the accelerator but also the color developing agent and other components in the developer into the mordanting agent-containing colloidal binder layer or into a layer adjacent thereto.

The present invention is illustrated in more detail below with reference to examples, but it is needless to say that the invention is not limited to the examples.

EXAMPLE 1 In this example is illustrated a photographic material comprising a photosensitive material and a dye transfer material which have individually been coated on separate supports.

The photosensitive material was prepared in the following manner.

To g. of an ordinary silver chlorobromide emulsion containing 10 g. of gelatin which had been obtained from l0 g of silver nitrate were added 8 g. of gelatin and 200 ml. of water. Subsequently, the emulsion was incorporated with 5 ml. of 2 percent chromium alumn, 1 ml. of a 10 percent formalin solution and 1.5 ml. of a 0.1 percent green-sensitizing dye. To the thus treated emulsion was added a solution formed by dissolving at 60C. 2 g of a yellow coupler splitting off magenta colored diffusible anionic dye-forming yellow in a solvent comprising 2 ml. of dimethylformamide, 20 ml. of a 1 percent triethylamine solution and 17 ml. of water. The emulsion was then incorporated with a small amount of a lN-NaOH solution to make the pH thereof 6.3 as well as to make the total amount thereof 500 g. Thereafter, the emulsion was coated on a baryta paper of 190 g/m so that the amount thereof became 80 glm On the resulting emulsion layer was further coated 50 g/m of a 3 percent gelatin solution as a protective layer, which was then dried to prepare the photosensitive material.

On the other hand, the dye transfer material was prepared in the following manner.

On a commercially available RC paper having a thin layer of white titanium-incorporated polyethylene on one side and a thin layer of transparent polyethylene on the other side was coated g/m of a 4 percent gelatin solution containing 3 g/liter of the aforesaid cationic high polymer mordanting agent having the structural formula (IX), followed by drying, to prepare the dye transfer material.

The photosensitive material was subjected to stepwise exposure through an optical wedge, and then dipped for 20 seconds (at 20C.) in a dark chamber in an activator solution formed by removing the developing agent from the standard color developer of the prescription shown in the table below. The dye transfer material was dipped for 30 seconds (at 20C.) in the color developer so as to sufficiently absorb the developer. Thereafter, the two materials were contacted face to face with each other. The resulting photographic material was carefully squeezed so that no air was interposed between the two materials. (In this case, it is convenient to utilize a developing machine for copying paper used in the silver salt diffusion transfer method.) Subsequently, the photographic material was allowed to stand at room temperature (20 to 23"C.) for 2, 5, l0 and 20 minutes, and then the photosensitive material was peeled off to find a magenta image which had been formed on the dye transfer material. The density of the said image was measured, and was then contrasted with the initial exposure amount (logarithmic gradation) to form such characteristic curves as shown by the broken lines in FIG. 3 which were the standards. From FIG. 3, it was understood that both density and gradation were not sufficient when the development dye transfer was conducted for 2 minutes, and the development dye transfer should be effected for at least about minutes, and that even when the development dye transfer time was prolonged to [0 and 20 minutes, the gradation (particularly at a density of below 1.2) scarcely changed, though the apparent sensitivity increased.

In view of the above, the development dye transfer time was limited to 2 minutes, and the photographic material was treated with each of 4 developers prepared by adding each 0.5, 1.0, 2.0 and 4.0 ml/liter of 1,6-diaminohexane to the color developer. As the result, there were formed such characteristic curves as shown by the solid lines in FIG. 3. in this case, the accelerator was not favorable in water solubility, so that l0 percent of water in the developer was replaced by ethanol. Accordingly, the above-mentioned curves ought to be compared with the curve of the blank sample represented by the dotted line. it should be noted that in the case of blank, the development was slightly inhibited due to the addition of alcohol to the developer, whereas in case 1.0 ml/liter of the accelerator according to the present invention was added, the gradation became close to that obtained in the standard minutes development dye transfer, and in case 2.0 ml/liter of the accelerator was added, the characteristic became similar to that obtained in the standard minutes development dye transfer. it should also be noted that in the standard 20 minutes development dye transfer, about 0.] of fog was formed, whereas in the above-mentioned case, no substantial fog was formed.

When the accelerator according to the present invention is used, the maximum density is considerably low, as mentioned previously. However, the density is a reflective density, so that the accelerator according to the present invention is favorably used for the development of monochromatic photographic material and is used sufficiently satisfactory for the development of color photographic material having three colored layers.

Prescriptions of standard color developer, activator, and accelerator-containing developer incorporated with 10 percent ethanol:

The results obtained in this example, when represented by the values of apparent sensitivity increase (AS) at a density of 0.5 in FIG. 3, were such that the AS values obtained in the standard treatment carried out for 5. l0 and 20 minutes were 0.34, 0.43 and 0.52, respectively, as compared with the case where the standard treatment was conducted for 2 minutes, whereas the values of apparent sensitivity increase (AS) obtained in the 2 minutes treatment using the accelerator were as shown in the following table:

Example i was repeated, except that the accelerator was replaced by each of l,2-diaminoethane (represented by C following the number of carbons; the same shall apply hereinafter), 1,3-diaminopropane (C 1,4-diaminobutane (C l,6 diaminohexane (C this overlaps the accelerator used in Example I), l,8- diaminooctane. and LlO-diaminodecane. For simplification, the results obtained were represented only by the values of apparent sensitivity increase (AS) and, for comparison, the concentration of the additives were represented by molar concentrations (mM), as shown in FIG. 1. From FIG. I, it is obvious that the addition of alcohol is advantageous, though there were some cases where no alcohol was added. Further, the accelcrating effect of l, l 0 diaminodecane (C is inferior in accelerating effect to that of C even when it is added to the developer incorporated with alcohol, but is still higher than those of C and C However, l,l2- diaminododecane (C not only shows no accelerating ability any more, even when added to the alcoholincorporated developer, but also strongly inhibits the development, even when used in a considerably small amount (0.6 mM), and its value of AS becomes negative and reaches 0.37.

It is also understood from FIG. 1 that the value of AS increases, within a certain range, in proportion to the concentration of additive, When each straight line is extended to intersect the horizontal axis, therefore, there is found such a limiting point that if the concentration of additive is at a position higher than the intersection, the additive shows a accelerating effect. Thus, the concentration at the intersection can be deemed as a limiting effective concentration. If the concentration of additive is lower than said limiting effective concentration, there is attained a favorable accelerating effect. A reciprocal of the said concentration can also be a measure for the evaluation of effectiveness.

EXAMPLE 3 --CH NH hereinafter abbreviated to 2E3A"),

dipropylenetriamine (Nl-I -CH CH CH N- H-CH -CH CH -NH hereinafter abbreviated to 2Pr3A) and triethyienetetramine (NH -(CH ---NH-(CH ---NH-(CH -NH hereinafter abbreviated to 3E4A") were individually added, while varying the concentrations, to each of developers incorporated and not incorporated with alcohol, as in Example 2, and the same development dye transfer as in Example 1 was effected. The results obtained were graphed to draw such characteristic curves as in FIG. 3. From these characteristic curves were calculated the values of apparent sensitivity increase (AS), which were then contrasted with the additive concentrations to form a graph similar to that shown in FIG. I. From the intersections of straight lines passing the measured points with the horizontal axis, there were calculated, in the same manner as described above, the limiting effective concentrations in terms of mM of the abovementioned three polymethylene-polyamines. Reciprocals of said mM values were combined with the case of Example 2, and the relation thereof with the number of carbons was graphed to draw the curves shown in FIG. 2 (for reference, the limiting effective concentrations are also graduated on the right side of FIG. 2). In the case of the simple diamines shown in FIG. 1, the accelerating effects linearly increase in proportion to the number of carbon atoms up to 8, and thereafter quickly decrease. In the case of the triamines and tetramine of this example, the accelerating effects do not increase in proportion to the number of carbon atoms. For exam ple, in the case of 3E4A, the numbers of carbon chains between NH; and NH, as measured by considering that NH is also identical with CH are 2, and 8, as shown below.

or white square in FIG. 2. In the case of 2E3A also, it

is considered that the corresponding carbon number is 3.5. In the case of 2Pr3A, which has a corresponding carbon number of 5, the limiting effective concentration thereof is above the straight line when no alcohol has been added, and is below the straight line when alcohol has been added. This is considered ascribable to the point that in the aqueous system, 2Pr3A displays an action similar to that of a polyamine small in number of carbon chains, while in the alcohol-incorporated system, it displays an action similar to that of a polyamine large in number of carbon chains. This not only shows that the above-mentioned idea of corresponding car bon chains is substantially correct, but also clarifies the relation between the effects of said polymethylenepolyamines as accelerator and the molecular structures thereof.

EXAMPLE 4 The same commercially available RC paper as in Example l was subcoated with about 80 g/m of a solution of the composition shown below to form a neutralization layer.

Vinyl methyl ether-maleic anhydride copolymer (Commercially available PVM/MA produced by Mitsubishi Chemical Co.) 5 Polyvinyl alcohol l0 Gelatin l2 Ascorbic acid 0 Water (neutralized with alkali to pH 4.0) to make the total amount Separately, l2 g. of the aforesaid cationic high polymer mordanting agent of the structural formula (V) was dissolved in 240 ml. of water, and the resulting solution was heated to 50C. This solution was poured in the form of a fine stream with stirring into a solution kept at 250C, which had been formed by dissolving 24 g. of a commercially available gelatin phthalate (a compound obtained by substituting 98 percent of the reactive e-amino groups of gelatin with phthalic acid; produced by Liner Co. of Britain) and 32 g. of ordinary gelatin in 480 ml. of water. After 4 minutes, when fine coaservate particles had completely been formed by the reaction of the anionic gelatin phthalide with the cationic polymer, 5.0 ml. of a 20 percent formaldehyde solution was added. Thereafter, the liquid was aged with gradual stirring at 50C. for 1 hour to form a coaservate dope (total amount 800 g). 200 Grams of the coaservate dope was mixed with 200 g. ofa separately prepared 7 percent gelatin solution. To the resulting mixture was added 8 ml. ofa 4 percent saponin solution to form a mordanting agent-containing colloidal binder solution, the total amount of which was then made 500 g. by addition of water.

The thus formed colloidal binder solution was coated on the neutralization layer, which had been formed on the aforesaid RC paper, and then dried to prepare a dye transfer material. This dye transfer material was contacted face to face with the same photosensitive material as in Example I to prepare a photographic material. The thus prepared photographic material was subjected to development dye transfer for 2 minutes using the activator-incorporated standard color developer used in Example 1 to obtain a standard sample (a). In the same manner as above, the photographic material was treated with the standard developer incorporated with 5.0 g. of sodium thiosulfate (pentahydrate) per liter of the developer to obtain a sample (b); with the standard developer incorporated with 5.0 g. of sodium thiosulfate (pentahydrate) and 0.5 g. of hydroquinone per liter of the developer incorporated with 2.0 g. of l,2-diaminopropane per liter of the developer to obtain a sample ((1); and with the standard developer incorporated with 4.0 g. of 1,2-diaminopropane per liter of the developer to obtain a sample (e). The thus obtained samples were compared in apparent sensitivity increase (AS) and fog (F) with the standard sample (a) to obtain the values as shown in the following table:

Sample (a) (bi AS 0.28 0.41 0.37 0.60 F 0.00 0.20 0.35 0.02 0. l 3

From the above table, it is evident that the process of the present invention is excellent.

EXAMPLE 5 EXAMPLE 6 5 grams of the aforesaid cationic high polymer mordanting agent poly-(4-vinylpyridine)toluenesulfonate having the structural formula (Ii) and I g. of polyvinyl alcohol were dissolved in 501) ml. of water. To the resulting solution was added a solution of g. of 1,8- diaminooctane in 100 ml. of ethanol. The mixed solution was coated by use of an extrusion coater on a transparent triacetate film base in such an amount as to form a film having a dry thickness of about 3;; (i.e. 120

lm)v On the thus formed film, a solution (total amount 500 g.) containing g. of a polyvinyl pyrrolidone (PVP K-QO produced by GAF Co. of the United States), 25 g. of a percent polyacrylamide solution ("Kogam 20" produced by Kobunshi Kagaku K. R. t, l g. of a decolorizing dye (purplish brown color) and 5 g. of saponin was coated by use of an extrusion coater in such an amount as to form a film having a dry thickness of about 1.2a (i.e. 30 g/m). On the resulting film were precisely coated by use of an extrusion coater (1) a redsensitized silver chlorobromide emulsion incorporated with a non-diffusible yellow coupler splitting off diffusion cyan dye of the formula,

in which emulsion, 50 percent of the gelatin to be used had been replaced by carboxymethyl cellulose; (2) as an inter layer, a liquid prepared by adding 0.4 percent of a scavenger comprising a magenta dye-forming nondiffiisible coupler (which may be an optional nondiffusible coupler of the prior art) to an aqueous solution containing l percent of gelatin and 1 percent of carboxymethyl cellulose; (3) a green-sensitized silver chlorobromide emulsion incorporated with the same yellow non-diffu sible coupler splitting off diffusible magenta dye as used in Example 1, in which emulsion, 50 percent of the gelatin to be used had been replaced by carboxymethyl celluolose; (4) as an inter layer, a liquid of the same composition as in (2 (4) a silver chlorobromide emulsion having a peculiar blue sensitivity which had not particularly been color-sensitized and which had been incorporated with a colorless nondiffusible coupler splitting off yellow color of the structural formula,

l T can in which emulsion, 50 percent of the gelatin to be used had been replaced by carboxymethyl cellulose; and (6) as an over layer. a liquid of the same composition as in (2), in this order. followed by drying, to form a photosensitive material portion. in this photosensitive material portion. the composition and silver content of the emulsion, the amounts of the couplers used, the thickness of the individual films, etc. were identical with those in the case of a commercially available color paper, unless otherwise specified.

The finished photographic material obtained in the above manner is used for the printing of cinefilms, in general. but may be used for the printing of color slides and large sized transparent color photographs. That is, the photographic material is printed from a color negative. exposed to light, developed for 2 minutes in a vat,

like in the case of ordinary photographic material, with the developer used in Example 1 which had been freed from the 1,6-diaminohexane, and then washed with water, whereby the photosensitive material portion is washed off and only the dye transfer layer bearing a color positive image remains on h r 'is rent film base, so that it is sufficient to dry the dye transfer layer. Thus, the processing can be effected quickly, and the result can be observed mmediately. In the abovementioned development process, where no accelerator has been incorporated into the developing bath, however, the accelerator incorporated into the dye transfer layer not only diffuses in the photosensitive emulsion layer but also diffuses and dissolves in the developer, and when a cinefilm or the like long film is developed according to the above-mentioned development process, the accelerator accumlates in the developing bath. in order to obtain a definite result, therefore, the developing bath should have been incorporated with the accelerator, even when a suitable amount of the accelerator has already been added to the dye transfer layer. Moreover, the developing bath should always be strictly managed and renewed as it is fatigued. Thus, the above-mentioned development process is difficult for amateurs. It is therefore preferable to adopt such a process as mentioned below.

A development belt is separately prepared by thickly coating (to a dry thickness of about 2514) a 15 percent gelatin solution on a base (preferably an RC-base), which is substantially identical in elongation with the film base used, followed by drying. The thus prepared belt is dipped in the aforesaid developer (containing 10 percent ethanol but no accelerator) to sufficiently absorb the developer. Subsequently, the belt is super posed face to face with the aforesaid exposed film and then rolled up with care so that no air bubbles are disposed between the two, and the rolled film is allowed to stand at normal temperature for at least 2 minutes. In this case, the developer used for the development is always fresh, and a proper amount of the accelerator is supplied from the dye transfer layer. Moreover, the developer is used in a definite amount per definite area, so that the development is not substantially affected by time and temperature. Accordingly, the abovementioned process is not only easy for amateurs to obtain a definite result, but also advantageous for those skilled in the art. The rolled film is unrolled and then washed with water, whereby the photosensitive emulsion layer disperses and flows out in the water, so that the film can be projected immediately after drying. Since a suitable amount of the mordanting agent has been incorporated into the dye transfer material portion, the dye transfer can be effected quickly and a color positive image less in fog and definite in color tone and density can be obtained.

This example is described in Japanese Patent 561,456 (Japanese Patent Publication No. 16,101).

As the scavenger similar to coupler which prevents the oxidation product of developer formed in the devel opment of one photographic emulsion layer from diffusing into other layer to color this layer. in the present invention, however, even a colored coupler can be used so far as the dye formed therefrom does not diffuse. and therefore an optional non-diffusible coupler may be used.

EXAMPLE 7 A color film was prepared in the same manner as in Example 1. except that a high sensitivity silver iodobromide emulsion was used in place of the silver chlorobromide emulsion, and 50 percent of the gelatin in the photosensitive material portion had been replaced by carboxymethyl cellulose like in Example 6. This color film is particularly useful as an amateur cinefilm. That is, after photographing, the film is superposed face to face with the development belt of Example 6 which has absorbed a black-white developer, subjected to first development at 30C. for 7 minutes, peeled off from the belt, and then washed with 3 percent magnesium sulfate. During this time, both sides of the film are subjected to second exposure (for a total of 2 minutes) by irradiation with a 500 W lamp positioned at a distance of 30 cm. Subsequently, the film is again dipped in the same developer as in Example 1, except that 2.0 ml/liter of 1,4-diaminobutane has been used in place of the 1,6-diaminohexane to absorb the developer into the film, treated at 30C. for 3 minutes, and then washed with water to remove unnecessary photosensitive emulsion layer, whereby a color positive image high in gradation and density is left on the base. Accordingly, the film can be projected immediately after drying.

EXAMPLE 8 The same dye transfer layer as in Example 6 was coated, in the same manner as in Example 6, to a thickness of about 3pm on a polyester base to prepare a dye transfer material (in which 6 g. of l,6-diaminohexane had been contained as an accelerator in place of g. of the l ,S-diaminooctane).

On the other hand, 5 g. of an S0 double salt of Schiff's base of a color developing agent having the structural formula,

and o-sulfobenzaldehyde, and 25 g. of gelatin were dissolved in 500 ml. of water. The resulting solution was coated on a polyester base so that the amount of the solution became about 100 g/m. On the thus formed layer, 160 glm of a liquid prepared by adding 0.3 percent of an antihalation purplish brown dye to a percent gelatin solution was coated to form a layer. On this layer, a commercially available green-sensitized fine silver chlorobromide emulsion for microfilm, which has been incorporated with the yellow color non-diffusible coupler splitting off diffusible magenta dye used in Example l, was coated to a dry thickness of about Sp. to prepare a photosensitive material.

The photosensitive material was subjected to direct photographing, or to electronic recording or contact printing from other microfilm, and then dipped for 1 minute in the activator used in Example 1 to sufficiently absorb the activator. Immediately thereafter, the photosensitive material was closely contacted face to face with the dye transfer material, allowed to stand for 2 minutes and then peeled off, whereby a magenta colored micro image was obtained on the surface of the dye transfer material.

Ordinarily, an image obtained in a similar manner as above ought to be somewhat low in resolution, due to the diffusion of dye at the stage of dye transfer. However, the image obtained in this example was unexpectedly good in resolution due to the facts that the dye transfer material had contacted with the most sharp image on the surface of the photosensitive material, the film was thin, and the granularity of color image ascribable to the silver halide particles had substantially been disappeared. Moreover, the thus obtained image was a colored image, and hence had such characteristics that it was free from the drawback of white dot, which frequently comes into question during the storage in a dark place ofa silver image-bearing microfilm (i.e. the partial bleaching of silver image due to peroxides derived from containers and the like), and was higher in absorbancy index than a silver image.

In the present invention, the color is not limited to a magenta color, but may be a mixture of yellow and cyan colors. In the case of a microfilm for electronic video recording, it is desirable that the coupler is incorporated so as to be in conform to the spectral wave length characteristics of scanning light source used at the time of reproduction thereof.

What is claimed is:

l. [n a color development dye transfer method in which a color photograph is obtained quickly by using a dye transfer color photographic material comprising a portion composed mainly of a photosensitive silver halide emulsion layer containing a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling, in combination with a portion composed mainly of a dye transfer layer containing a cationic higher polymer mordanting agent layer capable of fixing therein the diffused anionic dye, subjecting the photographic material to exposure and color development to fix in the dye transfer layer the anionic dye splitted off by the coupling reaction, and then removing the unnecessary photosensitive emulsion layer portion therein by leaving the dye transfer layer in which a desired color image is formed, the improvement which comprises accelerating the dye transfer rate of color development by affecting dye transfer in the presence of a mixture of an alcohol and at least one of polymethylenepolyamine derivative having the general formula,

wherein R is a hydrogen atom or a lower alkyl group; and n, p and q are individually a positive integer of from 1 to 9, 2 to 4, and l to 4, respectively without directly introducing said polymethylenepolyamine derivative directly into said silver halide emulsion layer.

2. A dye tranfer color photographic material for use in the color development dye transfer photographic method described in claim 1 in which a dye transfer layer portion is formed on an independent support and is used in combination with a photosensitive emulsion layer portion formed on other support, and at least one of the polymethylenepolyamine derivatives set forth in claim 1 has been incorporated in a total of 0.03 to 2 g. per in of the finished dye transfer layer into the mordanting agent-containing colloidal binder layer of the material or into a layer adjacent thereto.

3. The method of claim 1 wherein said alcohol is ethanol.

4. The method of claim 1 wherein said polymethylenepolyamine derivative is contained in a developer composition in an amount of 0.15 to 3.0 g/liter.

S. The method of claim 4, wherein said developer so lution further contains water and an alkali compound sufficient to form an aqueous alkaline developer solution.

6. A dye transfer color photographic material for use in the color development dye transfer photographic method described in claim 1 which has such a structure that a dye transfer layer portion and a photosensitive silver halide emulsion layer portion have been coated on one support together with auxiliary layers so that before the exposure and development dye transfer treatment, the two portions are in a unified state and, after the development dye transfer treatment, the photosen' sitive emulsion layer portion is removed, if necessary together with the auxiliary layers, in which said mate rial comprises as a set, a photosensitive silver halide emulsion layer, a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling with a developing agent and a mordant layer containing a cationic high polymer between which an inter hydrophilic colloide layer is interposed, characterized in that at least one of the polymethylenepolyamine derivatives set forth in claim 1 has been incorporated in a total of 0.03 to 2 g. per m of the photographic material into a layer other than said silver halide photosensitive layer. 

1. In a color development dye transfer method in which a color photograph is obtained quickly by using a dye transfer color photographic material comprising a portion composed mainly of a photosensitive silver halide emulsion layer containing a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling, in combination with a portion composed mainly of a dye transfer layer containing a cationic higher polymer mordanting agent layer capable of fixing therein the diffused anionic dye, subjecting the photographic material to exposure and color development to fix in the dye transfer layer the anionic dye splitted off by the coupling reaction, and then removing the unnecessary photosensitive emulsion layer portion therein by leaving the dye transfer layer in which a desired color image is formed, the improvement which comprises accelerating the dye transfer rate of color development by affecting dye transfer in the presence of a mixture of an alcohol and at least one of polymethylenepolyamine derivative having the general formula,
 1. IN A COLOR DEVELOPMENT DYE TRANSFER METHOD IN WHICH A COLOR PHOTOGRAPH IS OBTAINED QUICKLY BY USING A DYE TRANSFER COLOR PHOTOGRAPHIC MATERIAL COMPRISING A PORTION COMPOSED MAINLY OF A PHOTOSENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING A NON-DIFFUSIBLE COUPLER CAPABLE OF SPLITTING OFF A DIFFUSIBLE ANIONIC DYE BY COUPLING, IN COMBINATION WITH A PORTION COMPOSED MAINLY OF A DYE TRANSFER LAYER CONTAINING A CATIONIC HIGHER POLYMER MORDANTING AGENT LAYER CAPABLE OF FIXING THEREIN THE DIFFUSED ANIONIC DYE, SUBJECTING THE PHOTOGRAPHIC MATERIAL TO EXPOSURE AND COLOR DEVELOPMENT TO FIX IN THE DYE TRANSFER LAYER THE ANIONIC DYE SPLITTED OFF BY THE COUPLING REACTION, AND THEN REMOVING THE UNNECESSARY PHOTOSENSITIVE EMULSION LAYER PORTION THEREIN BY LEAVING THE DYE TRANSFER LAYER IN WHICH A DESIRED COLOR IMAGE IS FORMED, THE IMPROVEMENT WHICH COMPRISES ACCELERATING THE DYE TRANSFER RATE OF COLOR DEVELOPMENT BY AFFECTING DYE TRANSFER IN THE PRESENCE OF A MIXTURE OF AN ALCOHOL AND AT LEAST ONE OF POLYMETHYLENEPOLYAMINE DERIVATIVE HAVING THE GENERAL FORMULA,
 2. A dye tranfer color photographic material for use in the color development dye transfer photographic method described in claim 1 in which a dye transfer layer portion is formed on an independent support and is used in combination with a photosensitive emulsion layer portion formed on other support, and at least one of the polymethylenepolYamine derivatives set forth in claim 1 has been incorporated in a total of 0.03 to 2 g. per m2 of the finished dye transfer layer into the mordanting agent-containing colloidal binder layer of the material or into a layer adjacent thereto.
 3. The method of claim 1 wherein said alcohol is ethanol.
 4. The method of claim 1 wherein said polymethylenepolyamine derivative is contained in a developer composition in an amount of 0.15 to 3.0 g/liter.
 5. The method of claim 4, wherein said developer solution further contains water and an alkali compound sufficient to form an aqueous alkaline developer solution.
 6. A dye transfer color photographic material for use in the color development dye transfer photographic method described in claim 1 which has such a structure that a dye transfer layer portion and a photosensitive silver halide emulsion layer portion have been coated on one support together with auxiliary layers so that before the exposure and development dye transfer treatment, the two portions are in a unified state and, after the development dye transfer treatment, the photosensitive emulsion layer portion is removed, if necessary together with the auxiliary layers, in which said material comprises as a set, a photosensitive silver halide emulsion layer, a non-diffusible coupler capable of splitting off a diffusible anionic dye by coupling with a developing agent and a mordant layer containing a cationic high polymer between which an inter hydrophilic colloide layer is interposed, characterized in that at least one of the polymethylenepolyamine derivatives set forth in claim 1 has been incorporated in a total of 0.03 to 2 g. per m2 of the photographic material into a layer other than said silver halide photosensitive layer. 